Organosilicon Chemistry

Tamejiro Hiyama, PhD, is RDI Fellow at Chuo University and Professor Emeritus at Kyoto University (both in Japan). He is best known for his work in developing the Nozaki-Hiyama-Kishi reaction and the Hiyama cross-coupling. He is the recipient of the Chemical Society Award, the Humboldt Research Award, and the Frederic Stanley Kipping Award in Silicon Chemistry, and has published over 500 papers and 25 books.Martin Oestreich, PhD, is Einstein Professor of Synthesis and Catalysis at the Technische Universität Berlin, Germany. His research is focused on main-group chemistry related to catalysis with emphasis on silicon and boron. He is on the editorial advisory board of European Journal of Organic Chemistry, Chemical Society Reviews, and Chemical Science, and has published over 250 papers and five books.

• Foreword xiiiPreface xv1 Catalytic Generation of Silicon Nucleophiles 1Koji Kubota and Hajime Ito1.1 Introduction 11.2 Silicon Nucleophiles with Copper Catalysts 21.2.1 Copper-Catalyzed Nucleophilic Silylation with Disilanes 21.2.1.1 Silylation of α,β-Unsaturated Carbonyl Compounds 21.2.1.2 Silylation of Alkylidene Malonates 31.2.1.3 Silylation of Allylic Carbamates 31.2.2 Copper-Catalyzed Nucleophilic Silylation with Silylboronate 41.2.2.1 Silicon–Boron Bond Activation with Copper Alkoxide 41.2.2.2 Silylation of α,β-Unsaturated Carbonyl Compounds 41.2.2.3 Catalytic Allylic Silylation 71.2.2.4 Catalytic Silylation of Imines 91.2.2.5 Catalytic Silylation of Aldehydes 91.2.2.6 Catalytic Synthesis of Acylsilanes 111.2.2.7 Silylative Carboxylation with CO2 111.2.2.8 CO2 Reduction via Silylation 131.2.2.9 Silyl Substitution of Alkyl Electrophiles 131.2.2.10 Decarboxylative Silylation 141.2.2.11 Silylative Cyclization 151.2.2.12 Silylative Allylation of Ketones 151.2.2.13 Silylation of Alkynes 161.2.2.14 Propargylic Substitution 191.2.3 Copper-Catalyzed Nucleophilic Silylation with Silylzincs 201.3 Silicon Nucleophiles with Rhodium Catalysts 211.3.1 Rhodium-Catalyzed Nucleophilic Silylation with Disilanes 211.3.2 Rhodium-Catalyzed Nucleophilic Silylation with Silylboronates 211.3.2.1 Conjugate Silylation 211.3.2.2 Coupling between Propargylic Carbonates to Form Allenylsilanes 221.4 Silicon Nucleophiles with Nickel Catalysts 221.4.1 Nickel-Catalyzed Nucleophilic Silylation with Alkyl Electrophiles 221.5 Silicon Nucleophiles with Lewis Base Catalysts 231.5.1 N-Heterocyclic Carbene-Catalyzed Nucleophilic 1,4-Silylation 231.5.2 Alkoxide Base–Catalyzed 1,2-Silaboration 241.5.3 Phosphine-Catalyzed 1,2-Silaboration 241.6 Closing Remarks 25Abbreviations 25References 262 Si─H Bond Activation by Main-Group Lewis Acids 33Dieter Weber and Michel R. Gagné2.1 Introduction to Silanes and the Si─H bond 332.1.1 Overview of the Discovery and the History of Silanes 332.1.2 A Comparison of Hydrocarbons and Hydrosilicons 342.1.3 Stability of the Silicon–Hydrogen Bond 352.1.4 The Silylium Ion 352.2 The Activation of Si─H Bonds by Boron Lewis Acids 362.2.1 Tris(pentafluorophenyl)borane (BCF) 362.2.2 The Catalytic Activation of Si─H Bonds by BCF and Other Boranes 362.2.2.1 The Mechanism of Borane-Catalyzed Si─H Bond Activation 362.2.2.2 Additional Mechanistic Aspects 382.2.3 Categorizing Reduction Types of π and σ Bonds Involving the η1-[B]–H–[Si] Adduct 402.2.3.1 Type I: The Reduction of Polar π Bonds (El═Nu/El≡Nu) 402.2.3.2 Type II: The Reduction of Polar σ Bonds (El–Nu) 452.2.3.3 Type III: The Reduction of Nonpolar π Bonds (A═A/A≡A) 552.2.3.4 Type IV: The Reduction of Nonpolar σ Bonds (A─A) 582.2.3.5 Combination of Reduction Types 612.2.3.6 Mechanistic Variation of Reduction Types 662.3 The Activation of Si─H Bonds by Aluminum Lewis Acids 722.4 The Activation of Si─H Bonds by Group 14 Lewis Acids 732.4.1 Introduction 732.4.2 Carbocations as Lewis Acids 732.4.3 Cationic Tri-coordinate Silylium Ions and Neutral Si(IV) Lewis Acids 742.5 The Activation of Si─H Bonds by Phosphorous-Based Lewis Acids 752.5.1 P(III) Lewis Acids 752.5.2 P(V) Lewis Acids 762.6 Summary and Conclusions 76Acknowledgments 77References 773 Si─H Bond Activation by Transition-Metal Lewis Acids 87Georgii I. NikonovReferences 1114 Metal–Ligand Cooperative Si─H Bond Activation 115Francis Forster and Martin Oestreich4.1 Introduction 1154.2 Cooperative Si─H Bond Activation with Carbene Complexes Across M─C Double Bonds 1164.3 Cooperative Si─H Bond Activation at M─N Bonds 1164.4 Cooperative Si─H Bond Activation at M─O Bonds 1174.5 CooperativeSi─H Bond Activation at M─S Bonds 1184.5.1 Introduction 1184.5.2 Seminal Results in Cooperative Si─H Bond Activation Across M─S Bonds 1194.5.3 Dehydrogenative C─H Silylation 1234.5.4 Competing Dehydrogenative Coupling and Hydrosilylation 1254.5.5 C─H Silylation by Hydrosilylation/Dehydrogenative Silylation/ Retro-Hydrosilylation 1264.6 Summary 127References 1285 Cationic Silicon-Based Lewis Acids in Catalysis 131Polina Shaykhutdinova, Sebastian Keess, and Martin Oestreich5.1 Introduction 1315.2 Deoxygenation and Hydrosilylation of C═X Multiple Bonds 1315.2.1 Deoxygenation of C═O Bonds 1315.2.2 Hydrosilylation of C═O, C═N, C═C, and C≡C Bonds 1335.3 C─F Bond Activation 1375.3.1 Hydrodefluorination 1375.3.2 Defluorination Coupled with Electrophilic Aromatic Substitution (SEAr) 1445.4 Friedel–Crafts C–H Silylation 1495.5 Diels–Alder Reactions 1535.6 Mukaiyama Aldol and Related Reactions 163References 1676 Transition-Metal-Catalyzed C─H Bond Silylation 171Yoshiya Fukumoto and Naoto Chatani6.1 C(sp)─H Bond Silylation 1716.2 C(sp2)─H Bond Silylation 1746.3 C(sp3)─H Bond Silylation 198References 2077 Transition-Metal-Free Catalytic C─H Bond Silylation 213David P. Schuman, Wen-Bo Liu, Nasri Nesnas, and Brian M. Stoltz7.1 Introduction 2137.2 Lewis Acid 2137.2.1 BCl3 Catalyst 2137.2.2 B(C6F5)3, a “Frustrated” Lewis Acid Catalyst 2147.2.3 Lewis Acid Conclusions 2227.3 Brønsted Acid 2227.4 Brønsted Base 2247.4.1 Early Example of Catalytic C–H Silylation by Brønsted Base 2247.4.2 Fluoride/Base Catalysis 2247.4.3 Brønsted Base–Catalyzed C–H Silylation of Alkynes 2267.5 Radical Dehydrosilylation 2297.5.1 “Electron” as a C–H Silylation Catalyst 2297.5.2 Discovery of Unusual KOt-Bu-Catalyzed C–H Silylation 2317.5.2.1 KOt-Bu-Catalyzed C–H Silylation Methodology 2327.5.2.2 Mechanistic Investigations of KOt-Bu-Catalyzed C–H Silylation and Related Chemistry 2347.6 C(sp3)–H Silylation 2387.7 Conclusion 238References 2398 Silyl-Heck, Silyl-Negishi, and Related Reactions 241Sarah B. Krause and Donald A. Watson8.1 Introduction 2418.1.1 Activation of Silicon–Halogen Bonds 2418.1.1.1 Oxidative Addition to Platinum Complexes 2428.1.1.2 Oxidative Addition to Palladium Complexes 2428.1.1.3 Oxidative Addition to Iridium and Rhodium Complexes 2438.2 Silyl-Heck Reactions 2448.2.1 Early Silyl-Heck Studies 2458.2.2 Multicomponent Coupling 2468.2.3 Improved Silyl-Heck Reaction Conditions 2478.2.4 Mechanistic Considerations 2528.2.5 Pre-catalyst Investigations 2548.2.6 The Formation of Silyl Ethers and Disiloxanes via the Silyl-Heck Reaction 2588.2.7 The Nickel-Catalyzed Silyl-Heck Reaction 2608.3 Silyl-Negishi Reactions 2638.4 Silyl-Kumada–Corriu Reactions 2678.5 Summary and Conclusions 268References 2699 Transition-Metal-Catalyzed Cross-coupling of Organosilicon Compounds 271Tamejiro Hiyama, Yasunori Minami, and Atsunori Mori9.1 Introduction 2719.1.1 Historical Background of the Cross-coupling with Organosilicon Reagents 2719.2 Improvements in the Cross-coupling Reaction of Organosilicon Compounds 2759.2.1 Ligand Design for the Palladium Catalyst 2759.2.2 Variation of Palladium Catalysts and Additive Systems 2769.2.3 Alternative Electrophiles and Metal Catalysts 2789.2.4 Cross-coupling Reaction of Functionalized Organosilicon Reagents 2849.2.5 Cross-coupling Reaction of Organosilanes Through Directed C─H Bond Activation 2859.2.6 Tandem Reaction Involving Silicon-Based Cross-coupling 2889.3 Cross-coupling of Silanols, Silanolates, Oligosiloxanes, and Polysiloxanes 2899.3.1 Silanols and Silanolates 2899.3.2 Disiloxanes, Oligosiloxanes, and Polysiloxanes 2949.4 Cross-coupling of Allylsilane, Arylsilanes, and Trialkylsilanes 2969.4.1 Silacyclobutyl, Allylsilanes, and Benzylsilanes 2969.4.2 Arylsilanes 3009.4.3 Trialkylsilanes 3049.4.4 2-Hydroxymethylphenyl(dialkyl)silanes 3139.5 Summary 323References 32310 Lewis Base Activation of Silicon Lewis Acids 333Sergio Rossi and Scott E. Denmark10.1 Introduction 33310.2 Direct Transfer of a Silicon Ligand to a Substrate Not Coordinated to the Silicon Atom 33810.2.1 Transfer of Hydride: Reduction of C═O and C═N Double Bonds Promoted by Trichlorosilane 33810.2.2 Reduction of Nitroaromatic Compounds by Trichlorosilane 35110.3 Direct Transfer of a Silicon Substituent to the Silicon-Coordinated Substrate 35310.3.1 Opening of Epoxides 35310.3.1.1 Lewis Base–Catalyzed Epoxide Opening with Chlorotrimethylsilane 35310.3.1.2 Lewis Base–Catalyzed Epoxide Opening with Silicon Tetrachloride 35510.3.2 Allylation of Substrates Using Allylic Trichlorosilanes 35910.3.2.1 Allylation of C═N Bonds 35910.3.2.2 Allylation of C═O Bonds 36110.3.3 Aldol Reactions Involving Preformed Enoxysilane Derivatives 37110.4 Interaction of the Silicon-Activated Substrate with an External Non-Coordinated Nucleophile 37510.4.1 Allylation of Aldehydes Mediated by Silicon Tetrachloride 37610.4.2 Aldol Reactions Involving Trialkylsilyl Enol Derivatives 37810.4.2.1 Aldol Reactions Involving Trialkylsilyl Enol Ether Derivatives 37810.4.2.2 Aldol Reactions Involving Trialkylsilyl Ketene Acetals 37910.4.2.3 Vinylogous Aldol Addition 38210.4.3 Synthesis of Nitrile Derivatives from Silyl Ketene Imines 38510.4.4 Passerini Reaction 38710.4.5 Phosphonylation of Aldehydes with Triethyl Phosphite 38810.5 Interaction of the Activated Substrate with an Externally Coordinated Nucleophile 39010.5.1 Direct Aldol Reactions and Double Aldol Reaction 39010.5.1.1 Direct Aldol Addition of Activated Thioesters 39510.5.2 Enantioselective Morita–Baylis–Hillman Reaction 39610.5.3 Outlook and Perspective 397Acknowledgment 398References 39811 Hydrosilylation Catalyzed by Base Metals 417Yusuke Sunada and Hideo Nagashima11.1 Introduction 41711.2 Base-Metal Catalysts for Hydrosilylation of Alkenes with Alkoxyhydrosilanes and Hydrosiloxanes 41811.2.1 Iron and Cobalt Catalysts 41911.2.1.1 Catalysts Bearing Tridentate Nitrogen Redox-Active Ligands and Related Catalysts 41911.2.1.2 Catalysts Containing CO, CNR, and NHC Ligands 42111.2.1.3 Miscellaneous 42511.2.2 Nickel Catalysts 42611.3 Hydrosilylation of Alkenes with Primary and Secondary Hydrosilanes by Base-Metal Catalysts 42711.4 Conclusion and Future Outlook 434References 43412 Silylenes as Ligands in Catalysis 439Yu-Peng Zhou and Matthias Driess12.1 Introduction 43912.2 Applications of Silylene Ligands in Catalysis 43912.2.1 Carbon–Carbon Bond-Forming Reactions 43912.2.2 Carbon–Heteroatom Bond-Forming Reactions 44512.2.3 Reduction Reactions 45112.3 Summary and Outlook 456Acknowledgment 457References 45713 Enantioselective Synthesis of Silyl Ethers Through Catalytic Si─O Bond Formation 459Amir H. Hoveyda and Marc L. Snapper13.1 Introduction 45913.2 Lewis Base–Catalyzed Enantioselective Silylations of Alcohols 46013.2.1 Early Lewis Base–Mediated Enantioselective Silylations of Alcohols 46013.2.2 Lewis– and Brønsted Base–Catalyzed Enantioselective Silylations of Polyols 46113.2.3 Directed Lewis Base–Catalyzed Enantioselective Silylations of Polyols 46913.2.4 Lewis Base–Catalyzed Enantioselective Silylations of Mono-Alcohols 47313.2.5 Lewis Base–Mediated Enantioselective Desilylations of Mono-Alcohols 47813.3 Brønsted Acid–Catalyzed Enantioselective Silylations of Alcohols 47913.4 Hydroxyl Group Silylations with Organometallic Complexes 48113.4.1 Directed, Catalytic Enantioselective Hydroxyl Group Silylations with Chiral Silanes 48213.4.2 Metal‐Catalyzed Enantioselective Hydroxy Group Silylations with Chiral Silanes 48613.4.3 Directed, Enantioselective Catalytic Hydroxy Group Silylations with Achiral Silanes 48713.4.4 Enantioselective Catalytic Hydroxyl Group Silylations with Achiral Silanes 48813.5 Conclusions 490References 49114 Chiral Silicon Molecules 495Kazunobu Igawa and Katsuhiko Tomooka14.1 Introduction 49514.1.1 General Background of Chiral Silicon Molecules 49514.1.2 History of Chiral Silicon Molecules 49614.2 Preparation of Enantioenriched Chiral Silicon Molecules 49714.2.1 Classification of Preparation Methods for Enantioenriched Chiral Silicon Molecules 49714.2.2 Separation of Stereoisomers of Chiral Silicon Molecules 49814.2.2.1 Classification of Separation Methods for Stereoisomers of Chiral Silicon Molecules 49814.2.2.2 Separation of Silicon Epimers of Chiral Silicon Molecules 49914.2.2.3 Kinetic Resolution of Enantiomers of Chiral Silicon Molecules 50014.2.3 Asymmetric Synthesis of Chiral Silicon Molecules 50314.2.3.1 Classification of Asymmetric Synthetic Methods for Chiral Silicon Molecules 50314.2.3.2 Desymmetrization of Prochiral Silicon Atoms by Substitution of a Heteroatom Substituent 50314.2.3.3 Desymmetrization of Dihydrosilane 50614.2.3.4 Desymmetrization of Prochiral Silicon Atoms by Enantioselective Substitution of a Carbon Substituent 50714.2.3.5 Desymmetrization of Prochiral Silicon Atoms by Transformations of Carbon Substituent(s) without Si─C Bond Cleavage 51314.3 Stereoselective Transformation of Enantioenriched Chiral Silicon Molecules 51514.3.1 Classification of Stereoselective Transformation of Chiral Silicon Molecules 51514.3.2 Nucleophilic Substitution at a Chiral Silicon Center 51514.3.3 Electrophilic Substitution at Chiral Silicon Center 51814.3.4 Oxidation at Chiral Silicon Center 51914.3.4.1 Oxidation of Hydrosilane 51914.3.4.2 Oxidation of Alkenylsilane 52114.3.5 Multistep Functionalization of Chiral Silicon Molecules 52114.4 Application of Enantioenriched Chiral Silicon Molecules 52314.4.1 Classification of Applications of Chiral Silicon Molecules 52314.4.2 Application as Chiral Reagents 52314.4.3 Application as Chiral Materials 52514.4.3.1 Chiral Silicon Polymer 52514.4.3.2 Circular Polarized Luminescence of Chiral Silicon Molecules 52714.4.4 Applications as Bioactive Molecules 52714.5 Summary and Conclusions 528References 528Index 533